Densely-packed films of lanthanide oxide nanoparticles via electrophoretic deposition

Abstract

A method of forming a film of lanthanide oxide nanoparticles. In one embodiment of the present invention, the method includes the steps of: (a) providing a first substrate with a conducting surface and a second substrate that is positioned apart from the first substrate, (b) applying a voltage between the first substrate and the second substrate, (c) immersing the first substrate and the second substrate in a solution that comprises a plurality of lanthanide oxide nanoparticles suspended in a non-polar solvent or apolar solvent for a first duration of time effective to form a film of lanthanide oxide nanoparticles on the conducting surface of the first substrate, and (d) after the immersing step, removing the first substrate from the solution and exposing the first substrate to air while maintaining the applied voltage for a second duration of time to dry the film of lanthanide oxide nanoparticles formed on the conducting surface of the first substrate.

Description

CROSS-REFERENCE TO RELATED PATENT APPLICATION

This application is a continuation-in-part of U.S. patent application Ser. No. 12/587,401, filed on Oct. 5, 2009, entitled “Electrophoretic Fabricated Feedstranding All-Nanoparticle Thin Film Materials” by Saad Hasan and James Dickerson, which is incorporated herein by reference in its entirety.

Some references, which may include patents, patent applications and various publications, are cited in a reference list and discussed in the description of this invention. The citation and/or discussion of such references is provided merely to clarify the description of the present invention and is not an admission that any such reference is “prior art” to the invention described herein. All references listed, cited and/or discussed in this specification are incorporated herein by reference in their entireties and to the same extent as if each reference was individually incorporated by reference. In terms of notation, hereinafter, bracketed “n” represents the nth reference cited in the reference list. For example, [71] represents the 71st reference cited in the reference list, namely, [71] S. V. Mahajan and J. H. Dickerson, Nanotechnology 18, 325605 (2007).

FIELD OF THE INVENTION

The present invention relates generally to films of nanoparticles, in particular, to films of lanthanide oxide nanoparticles and methods of forming same.

BACKGROUND

Lanthanide oxides such as europium oxide (Eu₂O₃) and gadolinium oxide (Gd₂O₃) are known for their light emitting and high-K dielectric properties, respectively [76, 58, 77]. The Eu³⁺-doped Gd₂O₃, in microcrystalline form, has been employed in video displays and tri-color fluorescent lamps as a red phosphor [78]. Recently, nanocrystalline form of Eu³⁺-doped sesquioxides has gained research interest due to their potential use in luminescent biological tags, efficient light emitting devices, and high-resolution displays. Gd₂O₃ has received research attention because of its high-κ dielectric properties. Gd₂O₃ has been proposed as silicon dioxide replacement for gate oxide in ultra-small complementary metal-oxide-semiconductor (CMOS) devices [77]. Most applications of luminescent and dielectric materials require their implementation in thin-film form. The Eu₂O₃ and Gd₂O₃ nanocrystals, made via colloidal techniques, need to be assembled into thin-film form to study their optical and dielectric properties.

Therefore, a heretofore unaddressed need exists in the art to address the aforementioned deficiencies and inadequacies.

SUMMARY OF THE INVENTION

In one aspect, the present invention relates to a method of forming a film of lanthanide oxide nanoparticles. In one embodiment, the method includes the steps of: (a) providing a first substrate with a conducting surface and a second substrate that is positioned apart from the first substrate, (b) applying a voltage between the first substrate and the second substrate, (c) immersing the first substrate and the second substrate in a solution that comprises a plurality of lanthanide oxide nanoparticles suspended in a non-polar solvent or apolar solvent for a first duration of time effective to form a film of lanthanide oxide nanoparticles on the conducting surface of the first substrate, and (d) after the immersing step, removing the first substrate from the solution and exposing the first substrate to air while maintaining the applied voltage for a second duration of time to dry the film of lanthanide oxide nanoparticles formed on the conducting surface of the first substrate.

In one embodiment, the first substrate is gold-coated glass, gold-coated silicon, stainless steel (316L), indium-tin-oxide (ITO)-coated glass, or doped silicon.

In one embodiment, the applied voltage, V, is in the range of 0 volts<V≦1000 volts.

In one embodiment, the non-polar solvent or apolar solvent includes at least one of hexane, octane and mixtures thereof, and each of the first duration of time, T1 and the second duration of time voltage, T2, is in the range of 0 minutes<T1, T2≦30 minutes.

In one embodiment, the first duration of time, T1 and the second duration of time voltage, T2, can be same or different.

In one embodiment, the solution has a concentration ranging from about 1×10¹⁴ nanoparticles per cubic centimeter to about 10×10¹⁵ nanoparticles per cubic centimeter.

In one embodiment, the film of lanthanide oxide nanoparticles formed on the conducting surface of the first substrate has a thickness ranging from about 50 to about 500 nm.

In one embodiment, the film of lanthanide oxide nanoparticles formed on the conducting surface of the first substrate has randomly close-packed lanthanide oxide nanoparticles with a packing density of about 66%.

In one embodiment, the lanthanide oxide nanoparticles are europium oxide (Eu₂O₃) nanoparticles or gadolinium oxide (Gd₂O₃) nanoparticles.

In yet another embodiment, the lanthanide oxide nanoparticles have a core diameter ranging from about 2 to about 3 nm.

In a further embodiment, the lanthanide oxide nanoparticles are surface-passivated with oleic acid.

In another aspect, the present invention provides an article of manufacture having a film of the lanthanide oxide nanoparticles made by the method set forth immediately above.

In yet another aspect, the present invention relates to a metal-oxide-semiconductor (MOS) capacitor. In one embodiment, the MOS capacitor has: (a) a silicon substrate having a first surface, (b) a film of lanthanide oxide nanoparticles formed on the first surface of the silicon substrate using the method set forth immediately above, and (c) an aluminum film formed on the film of lanthanide oxide nanoparticles, wherein the film of lanthanide oxide nanoparticles comprises randomly close-packed lanthanide oxide nanoparticles with a packing density of about 66%.

In one embodiment, the silicon substrate has p-type silicon.

In one embodiment, the first surface of the silicon substrate is a p−(100) surface of silicon.

In one embodiment, the MOS capacitor further has a film of silicon oxide disposed between the silicon substrate and the film of lanthanide oxide nanoparticles.

In one embodiment, the lanthanide oxide nanoparticles have europium oxide (Eu₂O₃) nanoparticles or gadolinium oxide (Gd₂O₃) nanoparticles.

In another embodiment, the film of lanthanide oxide nanoparticles has a thickness ranging from about 50 to about 500 nm.

In yet another embodiment, the aluminum film has a thickness of about 300 nm.

In a further embodiment, the aluminum film is formed on the film of lanthanide oxide nanoparticles using electron-beam evaporation.

These and other aspects of the present invention will become apparent from the following description of the preferred embodiment taken in conjunction with the following drawings and their captions, although variations and modifications therein may be affected without departing from the spirit and scope of the novel concepts of the disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows: (a) TEM image of Eu₂O₃ nanocrystals, indicating an average diameter of about 2.4 nm; inset: electron diffraction pattern of the nanocrystals, exhibiting features arising from the {222} and {440} lattice planes; (b) absorption spectrum of the Eu₂O₃ nanocrystals, exhibiting strong absorption in UV region due to a transition from the ground state to the charge-transfer state of the Eu—O bond and (inset) a weak absorption peak at 395 nm due to the 4f→4f transition; and (c) photoluminescence spectrum of the nanocrystals, exhibiting peaks arising due to ⁵D₀→⁷F_J (J=0-4) transitions.

FIG. 2 shows: (a) optical micrograph of the Eu₂O₃ film deposited on a gold substrate, which appears golden in colour because of the background gold substrate and the high transparency of the film; (b) EDS spectrum of the film deposited on a gold substrate, which reveals the presence of europium, oxygen and carbon that originates from the oleic-acid-functionalized Eu₂O₃ nanocrystals and the gold from the substrate; and (c) PL spectra of the Eu₂O₃ nanocrystal films deposited on the anode and cathode. The spectra are identical to the spectrum of the Eu₂O₃ nanocrystals. PL spectra are shifted vertically for clarity.

FIG. 3 shows: (a) SEM image of the nanocrystal film; and (b) AFM image of the nanocrystal film, which reveals deposition of the nanocrystal agglomerates of about 15 nm size. RMS roughness of the film determined from the AFM image is 1.4 nm.

FIG. 4 shows: (a) optical micrograph of the patterned silicon substrate recorded through the nanocrystal film deposited on ITO-coated glass substrate, which reveals high transparency of the EPD film; and (b) transmission spectrum of a cast film of the Eu₂O₃ nanocrystals, showing high transparency in the visible region.

FIG. 5 shows the thickness of the EPD film as a function of the applied voltage for different nanocrystal concentrations. Average film thickness is reported from the thickness measurements at different locations and standard deviation is employed as the error bar. The large error bar indicates decreased film uniformity.

FIG. 6 shows the electrophoretic mobility measurements of the EPD suspensions with different nanocrystal concentrations.

FIG. 7 shows AFM images ((a), (b), (c), and (d)) and EDS spectrum ((e), (f), (g), and (h)) of the nanocrystal films deposited with the nanocrystal suspension concentration of 4×10¹⁵ NC cm⁻³ at the applied voltages of 250 V, 500 V, 750 V and 1000 V, respectively. The AFM images of the films reveal the agglomerate size of about 130-160 nm and RMS roughness of about 1.6-1.8 nm. The morphology and composition of the films were comparable.

FIG. 8 shows: (a) a schematic of the MOS capacitor structures with NC film as the gate oxide layer according to one embodiment of the present invention; (b) AFM image of the NC film (1 μm² area, height: 20 nm/div) with RMS roughness of about 1.6 nm; inset: TEM image of the about 2.4 nm diameter Gd₂O₃ nanocrystals (Image: 6 nm×6 nm); (c) EDS spectrum of the NC film; and (d) SEM image (top view) of the MOS capacitor structures.

FIG. 9 shows C-V characteristics of the MOS capacitors, fabricated from NC films that were deposited on the anode and cathode according to one embodiment of the present invention. The thickness of the film was 116 nm±10 nm, and the average area of the capacitors was 1.96×10⁵ μm².

FIG. 10 shows C-V characteristics of the MOS capacitors with different thicknesses of the NC films (oxide layer) according to one embodiment of the present invention.

FIG. 11 shows a graph of capacitance versus inverse of NC film (oxide layer) thickness for four different MOS capacitors according to one embodiment of the present invention. The slope of the linear regression fit was proportional to the permittivity of the nanocrystal film and, hence, to the film's dielectric constant, κ=3.90.

DETAILED DESCRIPTION

The present invention is more particularly described in the following examples that are intended as illustrative only since numerous modifications and variations therein will be apparent to those skilled in the art. Various embodiments of the invention are now described in detail. Referring to the drawings, FIGS. 1-11, like numbers, if any, indicate like components throughout the views. As used in the description herein and throughout the claims that follow, the meaning of “a”, “an”, and “the” includes plural reference unless the context clearly dictates otherwise. Also, as used in the description herein and throughout the claims that follow, the meaning of “in” includes “in” and “on” unless the context clearly dictates otherwise. Moreover, titles or subtitles may be used in the specification for the convenience of a reader, which shall have no influence on the scope of the present invention. Additionally, some terms used in this specification are more specifically defined below.

DEFINITIONS

The terms used in this specification generally have their ordinary meanings in the art, within the context of the invention, and in the specific context where each term is used. Certain terms that are used to describe the invention are discussed below, or elsewhere in the specification, to provide additional guidance to the practitioner regarding the description of the invention. For convenience, certain terms may be highlighted, for example using italics and/or quotation marks. The use of highlighting has no influence on the scope and meaning of a term; the scope and meaning of a term is the same, in the same context, whether or not it is highlighted. It will be appreciated that same thing can be said in more than one way. Consequently, alternative language and synonyms may be used for any one or more of the terms discussed herein, nor is any special significance to be placed upon whether or not a term is elaborated or discussed herein. Synonyms for certain terms are provided. A recital of one or more synonyms does not exclude the use of other synonyms. The use of examples anywhere in this specification including examples of any terms discussed herein is illustrative only, and in no way limits the scope and meaning of the invention or of any exemplified term. Likewise, the invention is not limited to various embodiments given in this specification.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In the case of conflict, the present document, including definitions will control.

As used herein, “around”, “about” or “approximately” shall generally mean within 20 percent, preferably within 10 percent, and more preferably within 5 percent of a given value or range. Numerical quantities given herein are approximate, meaning that the term “around”, “about” or “approximately” can be inferred if not expressly stated.

As used herein, if any, the term “atomic force microscope (AFM)” or scanning force microscope (SFM) refers to a very high-resolution type of scanning probe microscope, with demonstrated resolution of fractions of a nanometer, more than 1000 times better than the optical diffraction limit. The term “microscope” in the name of “AFM” is actually a misnomer because it implies looking, while in fact the information is gathered or the action is taken by “feeling” the surface with a mechanical probe. The AFM in general has a microscale cantilever with a tip portion (probe) at its end that is used to scan the specimen surface. The cantilever is typically silicon or silicon nitride with a tip radius of curvature on the order of nanometers. When the tip is brought into proximity of a sample surface, forces between the tip and the sample lead to a deflection of the cantilever according to Hooke's law. The AFM can be utilized in a variety of applications.

As used herein, if any, the term “transmission electron microscopy (TEM)” refers to a microscopy technique whereby a beam of electrons is transmitted through an ultra thin specimen, interacting with the specimen as it passes through it. An image is formed from the electrons transmitted through the specimen, magnified and focused by an objective lens and appears on an imaging screen, a fluorescent screen in most TEMs, plus a monitor, or on a layer of photographic film, or to be detected by a sensor such as a CCD camera.

As used herein, if any, the term “scanning electron microscope (SEM)” refers to a type of electron microscope that images the sample surface by scanning it with a high-energy beam of electrons in a raster scan pattern. The electrons interact with the atoms that make up the sample producing signals that contain information about the sample's surface topography, composition and other properties such as electrical conductivity.

As used herein, if any, the term “energy dispersive X-ray spectroscopy (EDS or EDX)” refers to an analytical technique used for the elemental analysis or chemical characterization of a sample. It is one of the variants of X-ray fluorescence spectroscopy which analyzes X-rays emitted by the matter in response to being hit with charged particles such as electrons or protons, or a beam of X-rays. Its characterization capabilities are due in large part to the fundamental principle that each element has a unique atomic structure allowing X-rays that are characteristic of an element's atomic structure to be identified uniquely from one another.

As used herein, if any, the term “absorption spectroscopy” refers to spectroscopic techniques that measure the absorption of radiation, as a function of frequency or wavelength, due to its interaction with a sample. The sample absorbs energy, i.e., photons, from the radiating field. The intensity of the absorption varies as a function of frequency, and this variation is the absorption spectrum. Absorption spectroscopy is employed as an analytical chemistry tool to determine the presence of a particular substance in a sample and, in many cases, to quantify the amount of the substance present. Infrared and ultraviolet-visible (UV-Vis) spectroscopy are particularly common in analytical applications. The term “infrared spectroscopy” refers to absorption spectroscopy in the infrared spectral region; and the term “ultraviolet-visible (UV-Vis) spectroscopy” refers to absorption spectroscopy in the ultraviolet-visible spectral region.

As used herein, if any, the term “photoluminescence spectroscopy” refers to a contactless, nondestructive method of probing the electronic structure of materials. In this method, light is directed onto a sample, where it is absorbed and imparts excess energy into the material in a process called photo-excitation. One way this excess energy can be dissipated by the sample is through the emission of light, or luminescence. In the case of photo-excitation, this luminescence is called photoluminescence. The intensity and spectral content of this photoluminescence is a direct measure of various important material properties.

As used herein, if any, the term “C-V”, as in C-V profiling, or C-V measurements, or C-V characteristics, stands for capacitance-voltage, and refers to a technique used for characterization of semiconductor materials and devices. The technique uses a metal-semiconductor junction (Schottky barrier) or a p-n junction or a MOSFET to create a depletion region, a region which is empty of conducting electrons and holes, but may contain ionized donors and electrically active defects or traps. The depletion region with its ionized charges inside behaves like a capacitor. By varying the voltage applied to the junction it is possible to vary the depletion width. The dependence of the depletion width upon the applied voltage provides information on the semiconductor's internal characteristics, such as its doping profile and electrically active defect densities. Measurements may be done at DC, or using both DC and a small-signal AC signal (the conductance method), or using a large-signal transient voltage.

As used herein, the term “ITO” or “ITO glass” refers to indium tin oxide, or tin-doped indium oxide, which is a solid solution of indium(III) oxide (In₂O₃) and tin(IV) oxide (SnO₂), typically 90% In₂O₃, 10% SnO₂ by weight. It is transparent and colorless in thin layers while in bulk form it is yellowish to grey. In the infrared region of the spectrum it is a metal-like mirror. Indium tin oxide is one of the most widely used transparent conducting oxides and so has main feature of a combination of electrical conductivity and optical transparency. Thin films of indium tin oxide are most commonly deposited on surfaces by electron beam evaporation, physical vapor deposition, or a range of sputter deposition techniques.

As used herein, “nanoscopic-scale,” “nanoscopic,” “nanometer-scale,” “nanoscale,” “nanocomposites,” “nanoparticles,” the “nano-” prefix, and the like generally refers to elements or articles having widths or diameters of less than about 1 μm, preferably less than about 100 nm in some cases. In all embodiments, specified widths can be smallest width (i.e. a width as specified where, at that location, the article can have a larger width in a different dimension), or largest width (i.e. where, at that location, the article's width is no wider than as specified, but can have a length that is greater).

As used herein, “plurality” means two or more.

As used herein, the terms “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to.

OVERVIEW OF THE INVENTION

Lanthanide oxides such as europium oxide (Eu₂O₃) and gadolinium oxide (Gd₂O₃) are known for their light emitting and high-κ dielectric properties, respectively [76, 58, 77]. The Eu³⁺-doped Gd₂O₃, in microcrystalline form, has been employed in video displays and tri-color fluorescent lamps as a red phosphor [78]. Recently, nanocrystalline form of Eu³⁺-doped sesquioxides has gained research interest due to their potential use in luminescent biological tags, efficient light emitting devices, and high-resolution displays. Gd₂O₃ has received research attention because of its high-κ dielectric properties. Gd₂O₃ has been proposed as silicon dioxide replacement for gate oxide in ultra-small complementary metal-oxide-semiconductor (CMOS) devices [77]. Most applications of luminescent and dielectric materials require their implementation in thin-film form. The Eu₂O₃ and Gd₂O₃ nanocrystals, made via colloidal techniques, need to be assembled into thin-film form to study their optical and dielectric properties. Of the thin-film deposition techniques, electrophoretic deposition (EPD) is the promising technique to deposit nanomaterials. EPD offers a simple design set-up and provides substantial thickness control at high deposition rates to assemble particles site-selectively of any size and shape.

In one embodiment of the present invention, EPD technique is employed to deposit ultra-small (<3 nm) colloidal lanthanide oxide nanoparticles, specifically Eu₂O₃ and Gd₂O₃ nanocrystals, to form uniform, homogeneous films. The nanocrystals were synthesized via hot solution phase method and purified with ethanol prior to deposition [71]. The films were deposited onto conducting substrates such as gold-coated glass, gold-coated silicon, stainless steel (316L), indium-tin-oxide-coated (ITO) glass, and p-type silicon from a suspension of the nanocrystals in hexane.

A typical EPD involves the following sequence of the steps: application of a DC voltage to a pair of electrodes, insertion of the pair of electrodes into the EPD suspension (area: about 18 mm×13 mm), deposition for 15 min, and extraction of the pair of electrodes from the suspension, and drying in air for 5 min while maintaining the applied voltage. The films of different thicknesses were deposited employing different nanocrystal suspension concentrations (about 1-10×10¹⁵ NC/cc) and different applied voltages (about 250-1000 V).

Thus, in one aspect, the present invention provides a method of forming a film of lanthanide oxide nanoparticles. In one embodiment, the method comprises the steps of: (a) providing a first substrate with a conducting surface and a second substrate that is positioned apart from the first substrate, (b) applying a voltage between the first substrate and the second substrate, (c) immersing the first substrate and the second substrate in a solution that comprises a plurality of lanthanide oxide nanoparticles suspended in a non-polar solvent or apolar solvent for a first duration of time effective to form a film of lanthanide oxide nanoparticles on the conducting surface of the first substrate, and (d) after the immersing step, removing the first substrate from the solution and exposing the first substrate to air while maintaining the applied voltage for a second duration of time to dry the film of lanthanide oxide nanoparticles formed on the conducting surface of the first substrate.

In one embodiment, the first substrate is gold-coated glass, gold-coated silicon, stainless steel (316L), indium-tin-oxide (ITO)-coated glass, or doped silicon.

In one embodiment, the applied voltage, V, is in the range of 0 volts<V≦1000 volts.

In one embodiment, the non-polar solvent or apolar solvent includes at least one of hexane, octane and mixtures thereof, and each of the first duration of time, T1 and the second duration of time voltage, T2, is in the range of 0 minutes<T1, T2≦30 minutes.

In one embodiment, the first duration of time, T1 and the second duration of time voltage, T2, can be same or different.

In one embodiment, the solution has a concentration ranging from about 1×10¹⁴ nanoparticles per cubic centimeter to about 10×10¹⁵ nanoparticles per cubic centimeter.

In one embodiment, the film of lanthanide oxide nanoparticles formed on the conducting surface of the first substrate has a thickness ranging from about 50 to about 500 nm.

In one embodiment, the film of lanthanide oxide nanoparticles formed on the conducting surface of the first substrate comprises randomly close-packed lanthanide oxide nanoparticles with a packing density of about 66%.

In one embodiment, the lanthanide oxide nanoparticles are europium oxide (Eu₂O₃) nanoparticles or gadolinium oxide (Gd₂O₃) nanoparticles.

In yet another embodiment, the lanthanide oxide nanoparticles have a core diameter ranging from about 2 to about 3 nm.

In a further embodiment, the lanthanide oxide nanoparticles are surface-passivated with oleic acid.

In another aspect, the present invention provides an article of manufacture having a film of the lanthanide oxide nanoparticles made by the method set forth immediately above.

In yet another aspect, the present invention provides a metal-oxide-semiconductor (MOS) capacitor. In one embodiment, the MOS capacitor has: (a) a silicon substrate having a first surface, (b) a film of lanthanide oxide nanoparticles formed on the first surface of the silicon substrate using the method set forth immediately above, and (c) an aluminum film formed on the film of lanthanide oxide nanoparticles, wherein the film of lanthanide oxide nanoparticles comprises randomly close-packed lanthanide oxide nanoparticles with a packing density of about 66%.

In one embodiment, the silicon substrate has p-type silicon.

In one embodiment, the first surface of the silicon substrate is a p-(100) surface of silicon.

In one embodiment, the MOS capacitor further has a film of silicon oxide disposed between the silicon substrate and the film of lanthanide oxide nanoparticles.

In one embodiment, the lanthanide oxide nanoparticles include europium oxide (Eu₂O₃) nanoparticles or gadolinium oxide (Gd₂O₃) nanoparticles.

In another embodiment, the film of lanthanide oxide nanoparticles has a thickness ranging from about 50 to about 500 nm.

In yet another embodiment, the aluminum film has a thickness of about 300 nm.

In a further embodiment, the aluminum film is formed on the film of lanthanide oxide nanoparticles using electron-beam evaporation.

Additional details are set forth below.

EXAMPLES

Aspects of the present teachings may be further understood in light of the following examples, which should not be construed as limiting the scope of the present teachings in any way.

Example 1

Eu₂O₃ Nanocrystal Films.

The controlled assembly of nanomaterials into microscopic and macroscopic structures is one of the most important and continuously growing research directions in nanotechnology. Efficient bottom-up assembly approaches are essential to the development of next-generation optical, magnetic and electronic devices that utilize the unique properties of metallic, semiconducting or insulating nanomaterials. Currently employed nanomaterial assembly techniques include drop-casting, spin-casting [1], self-assembly [2-4], Langmuir-Blodgett [5, 6] and electrophoretic deposition (EPD) [7-9]. For an assembly technique to be commercially or industrially viable for the fabrication of nanostructured devices, the technique must involve flexibility of the type of material (metal/semiconductor/insulator), superior film thickness control, high rate of assembly and site-selectivity. Of the aforementioned deposition techniques, electrophoretic deposition is arguably the most promising for nanomaterial deposition, as EPD offers a simple design set-up and provides substantial thickness control at rapid deposition rates to assemble site-selectively particles of any size, shape and type [10]. EPD has been employed successfully to deposit films of metallic (Au, Pt) [11, 12], semiconducting (CdSe, ZnO) [7, 13], insulating (TiO₂, SiO₂, Eu₂O₃) [14-18] and magnetic (Fe₃O₄, Fe₂O₃) [9, 19] nanocrystals. Other types of nanomaterials, such as polymer nanoparticles [20, 21] and carbon nanotubes (CNTs) [9, 22-27], have been assembled_via EPD. Homogeneous and smooth films of nanocrystals have been reported for the nanocrystals functionalized with surface capping ligands such as CdSe, Fe₂O₃, Fe₃O₄ and Eu₂O_{3 [}7, 9, 16, 28]. Such nanocrystals form stable suspensions in non-polar solvents such as hexane because of the hydrophobic surface capping ligands, often used in colloidal nanocrystal syntheses to stabilize the surface of the nanocrystals [29-31]. Surface-stabilized Eu₂O₃ nanocrystal films have been of recent interest because of their strong ultraviolet (UV) absorption and the characteristic red colour emission of the nanocrystals [31]. Eu₂O₃ nanocrystal films have potential applications in UV absorption coatings, photoactive coatings and fluorescent screens [32, 33]. In these applications, the deposition of transparent films facilitates the efficient transmission of visible light. Since Eu₂O₃ nanocrystals have weak absorption in the visible, implementation of small-diameter, light-emitting nanocrystals should minimize light scattering losses and thereby enhance the transmission of light throughout the visible spectrum.

The relationship among the film thickness, the EPD suspension parameters (particle mobility) and the EPD process parameters (applied voltage, deposition time and nanocrystal concentration) was originally studied by Hamaker [34]. Later, the effect of these parameters on the deposition of various micron-sized ceramic particles (Al₂O₃, TiO₂, SiO₂) from their suspension in water and organic polar solvents was investigated [14, 15, 23, 35-40]. In contrast, research exploring the deposition of nanocrystals that are suspended in non-polar organic solvents (hexane) is relatively limited [7, 9, 19, 41]. Since the EPD suspension properties are dependent on the suspension medium, the properties for nanocrystals suspended in non-polar solvents differ from those of particles suspended in water and organic polar solvents. Nanocrystals with surface capping ligands form stable suspension in nonpolar solvent (e.g. hexane) because of the steric stabilization of the nanocrystal surface with ligands. Steric repulsive forces, developed between the nanocrystals by the ligands, overcome the van der Waals attraction forces to form the stable suspension [42]. The origin of surface charges in sterically stabilized nanocrystal suspensions also differs from that of electrostatically stabilized particles in suspension. In electrostatically stabilized systems, surface charges develop because of polar solvent molecules and free ions in the solvent [43, 44]. In contrast, the charges on the larger nanocrystals may originate from the adsorption of uncharged ligands, ion exchange between the adsorbed ligand and the surface, and desorption of the ionized ligands [45-47]. Thermal charging of nanocrystals in suspension has been another debated origin of charge [28, 48]. However, our most substantive concern regarding surface charge arises from charge tuning on the nanocrystals achieved through the addition of ligands and/or removal of ligands via purification steps [2]. Since a fraction of the ligands is detached during each step of nanocrystal purification, the nanocrystal surface charge can become changed. The effect of the number of nanocrystal purification steps on the quality of electrophoretically deposited CdSe nanocrystal films has been reported, which provides a considerable insight into the optimization of film quality [41]. Although studies have been conducted on the effect of EPD process parameters on the quality of films composed of micron-sized (or larger) electrostatically stabilized particles [49, 50], no specific report, to date, exists exploring the effect of EPD process parameters on the quality of sterically stabilized or electrostatically stabilized nanocrystalline films.

In various embodiments of the present invention, certain transparent films of Eu₂O₃ nanocrystals were fabricated via electrophoretic deposition and investigated the effect of EPD processing parameters (applied voltage, deposition time and nanocrystal concentration) on the uniformity of the films. About 2.4 nm Eu₂O₃ nanocrystals that were capped with oleic acid and were suspended in a non-polar solvent or apolar solvent such as hexane were employed. The films were deposited onto two types of substrates: gold-coated glass and indium-tin-oxide (ITO)-coated glass. The deposition of the nanocrystals on the anode and cathode was confirmed by conducting elemental analysis via energy dispersive spectroscopy (EDS) and optical analysis using photoluminescence spectroscopy (PL). Scanning electron microscopy (SEM) and atomic force microscopy (AFM) confirmed the deposition of homogeneous, topographically smooth films that were composed of densely packed agglomerates (about 15 nm) of the Eu₂O₃ nanocrystals. Additionally, the effect of EPD processing parameters on the thickness and uniformity of the transparent films were explored. The effect that these parameters had on the thickness homogeneity across the film provided a marked insight into the growth mechanisms of the films.

Nanocrystal Synthesis and Purification.

Europium oxide (Eu₂O₃) nanocrystals were synthesized via a two-stage solution-phase technique, as described in detail by the inventors elsewhere [31]. In the first stage, europium oleate was synthesized by heating a mixture of europium (III) chloride hexahydrate (EuCl₃.6H₂O) and sodium oleate (CH₃(CH₂)₇CH:CH(CH₂)₇COONa) at 70° C. for 4 hours in a hexane-ethanol-water mixture. Next, a mixture of europium oleate (0.5 mM) and oleic acid (0.25 mM) was heated to 350° C. in tri-n-octylamine (7 ml) and maintained at that temperature for an hour during the second stage. This synthesis yielded Eu₂O₃ nanocrystals of 2.4±0.3 nm core diameter, surface-passivated with oleic acid. The nanocrystals were isolated from the reaction mixture by a purification process that involved sequential precipitation and centrifugation sequences. The addition of ethanol to the reaction mixture facilitated nanocrystal precipitation; centrifugation helped to isolate the nanocrystals. The isolated nanocrystals were dispersed back into hexane and the precipitation-centrifugation sequence was repeated. The nanocrystals, purified four times (4×) by this procedure, were employed for transmission electron microscopy (TEM) imaging. The nanocrystals were purified further (10×) to deposit the optimum quality film. The final nanocrystal suspensions for employment in electrophoretic deposition were prepared in hexane.

Electrophoretic Deposition (EPD).

The EPD technique was used to deposit Eu₂O₃ nanocrystals onto two types of substrate: gold-coated glass (gold electrode) and indium-tin-oxide-coated glass (ITO electrode). Gold electrodes were fabricated by the thermal evaporation of about 20 nm of chromium, used as an adhesion layer, onto a glass substrate followed by about 125 nm of gold. ITO electrodes (surface-resistant: 15-25Ω) were purchased from Delta Technologies, Ltd. The electrodes were cut to the size of 25 mm×13 mm for EPD. Then, the electrodes were cleaned sequentially using acetone, ethanol and hexane with an intermediate drying step using a stream of nitrogen. The electrodes were mounted in a vertical parallel-plate configuration with a gap of about 5 mm. For a single EPD, a pair of the same type of substrate was employed as the positive and negative electrodes. A Keithley 6517A electrometer was utilized to apply DC bias to the electrodes and to measure current flowing through the suspension during the deposition. A typical EPD involved the following sequence: application of a DC voltage, insertion of an electrode pair into the EPD suspension (deposition area: about 18 mm×13 mm), deposition for 15 minutes, and extraction of the electrode pair from the suspension and drying in air for 5 minutes while maintaining the applied voltage.

Characterization.

The size of the Eu₂O₃ nanocrystals was measured from the image of the nanocrystals, acquired with a Philips CM 20 transmission electron microscope. The absorption and photoluminescence spectra of the nanocrystal suspensions were recorded using a Cary 5000 spectrophotometer and a Fluorolog-3-FL3-111 spectrophotofluorometer, respectively. Electrophoretic mobility of the nanocrystals was measured in suspension (hexane) from dynamic light scattering (DLS) experiments, performed on a Malvern Nano ZS system. Optical micrographs of the nanocrystal films were acquired with a Leitz microscope connected to a CFM-USB-2 camera from Angstrom Sun Technologies Inc. Surface morphologies of the films were analysed using a Hitachi S-4200 scanning electron microscope and a Digital Instruments Nanoscope III atomic force microscope in tapping mode. Deposition of the nanocrystals on the electrodes was confirmed by performing elemental analysis of the electrodes using energy dispersive spectroscopy with a Link ISIS Series 300 microanalysis system (Oxford Instruments). Film thickness using a Veeco Dektak 150 surface profiler was measured. The transmission and photoluminescence spectra of the nanocrystal films were acquired using a Cary 5000 spectrophotometer and a Fluorolog-3-FL3-111 spectrophotofluorometer, respectively.

Results and Implications.

FIG. 1 shows a TEM image and electron diffraction pattern of the Eu₂O₃ nanocrystals, and absorption and PL spectra of the nanocrystals that were dispersed in hexane. The average core diameter of the Eu₂O₃ nanocrystals was d_NC=2.4±0.3 nm, confirmed with the TEM image (as shown in FIG. 1(a). Shown as an inset to FIG. 1(a), an electron diffraction pattern of the nanocrystals revealed features attributable to the {222} and {440} lattice planes of Eu₂O₃. FIG. 1(b) shows the absorption spectrum of the nanocrystals. The nanocrystals exhibited strong absorption in the ultraviolet (UV) region but showed weak absorption in the visible region. The strong absorption peak at 225 nm was attributed to the transition between the ground state and the charge-transfer state of the Eu—O bond (4f⁷→4f⁷2p⁻¹) [51-53]. In addition, the weak absorption peak at 395 nm, shown in the inset to FIG. 1(b), arose from the 4f→4f transition [51]. FIG. 1(c) shows the photoluminescence spectrum of the nanocrystals upon UV excitation (254 nm). The peaks corresponded to the ⁵D₀→⁷F_J (J=0-4) radiative energy transitions within Eu³⁺ ions [31]. Of these characteristic transitions, the ⁵D₀→⁷F₂ is the most sensitive transition to the location of the Eu³⁺ ion within the crystal. The most intense PL peaks (612, 620 and 624 nm) were observed [31].

Known for its production of high quality films of colloidal nanocrystals, EPD was implemented to deposit the Eu₂O₃ nanocrystals from their suspension in hexane [9, 54]. Nanocrystal films were deposited on gold and ITO electrodes. FIG. 2(a) shows a typical optical micrograph of a Eu₂O₃ nanocrystal film, deposited on a gold electrode (anode). The nanocrystal film was cast with an applied voltage of 250 V and a nanocrystal concentration of 2×10¹⁵ NC cm⁻³. The yellowish colour of the film is due to its high transparency and the colour of the underlying gold substrate. The film was continuous with no visible defects larger than 5 μm. The film that was deposited on the cathode had a comparable appearance. The thickness of the film was about 110 nm, which was measured using surface profilometry. To verify deposition of Eu₂O₃ nanocrystals on the electrodes, EDS was performed for elemental analysis and PL for optical analysis. FIG. 2(b) shows the EDS spectrum of the nanocrystal film, deposited on the anode. The presence of europium, oxygen and carbon peaks confirmed the deposition of the oleic-acid-functionalized Eu₂O₃ nanocrystals. Also, gold was detected because of the underlying gold substrate. Similarly, deposition of the Eu₂O₃ nanocrystals was confirmed on the cathode. FIG. 2(c) shows the PL spectra of the anode and cathode upon UV excitation (254 nm). The spectra exhibited all of the peaks corresponding to the ⁵D₀→⁷F_J (J=0-4) energy transitions of the Eu³⁺ ion. The spectra were identical to the spectrum of the Eu₂O₃ nanocrystals (as shown in FIG. 1(c), confirming deposition of the Eu₂O₃ nanocrystals. Thus, the EDS and PL spectra of cathode and anode confirmed deposition of the Eu₂O₃ nanocrystal film.

Surface morphology of the nanocrystal film was probed with SEM and AFM. FIG. 3(a) shows the SEM image of the nanocrystal film, deposited on the anode. The nanocrystal film was topographically smooth and uniform. The film on the cathode had comparable surface morphology. AFM was employed to perform high-resolution surface topological analysis of the nanocrystal film. The AFM image, shown in FIG. 3(b), revealed that the film was composed of agglomerates of the Eu₂O₃ nanocrystals, approximately 15-20 nm in diameter. The apparent deposition of agglomerates of the nanocrystals instead of individual nanocrystals motivated us to identify the formation of any agglomerates in EPD suspension prior to the deposition. New TEM samples were prepared for imaging by drop-casting the EPD suspensions onto the grids. These new samples confirmed the absence of any agglomerates of the Eu₂O₃ nanocrystals in the EPD suspension. Thus, the agglomeration of the nanocrystals likely occurred under the influence of the electric field during EPD. The agglomeration may have occurred at one or more of the following stages: (a) immediate agglomeration upon application of the voltage to the electrodes in the EPD suspension; (b) agglomeration near the electrodes following an increase in the nanocrystal concentration due to movement of charged nanocrystals towards the respective electrodes and (c) reorganization of the deposited nanocrystals at the electrode leading to agglomeration. Even though the nanocrystals agglomerated under the influence of an electric field, the extent of agglomeration was limited because of sufficient ligand coverage on the nanocrystal surface. The deposited agglomerates packed close to each other, forming a continuous and densely arranged film (as shown in FIG. 3(b). It was reported a packing fraction of about 0.63 for random close packing, also known as glassy packing, of spheres [55]. The observed packing fraction (about 0.56) by practicing the present invention was calculated on the basis of the AFM image and was within the lower regime of glassy packing Nonetheless, these films were particularly smooth. The root mean square (RMS) surface roughness, determined from the AFM image of the film, was about 1.4 nm, which was smaller than the diameter of one nanocrystal. The two plausible reasons for the high smoothness of the films are: (a) a small fraction of the nanocrystals was deposited along with the agglomerates of the nanocrystals and (b) the agglomerates of the nanocrystals had a degree of structural flexibility since the nanocrystal surface was partially covered with ‘soft’ surface capping ligands. Thus, SEM and AFM imaging confirmed the formation of a smooth, uniform and densely packed film of the agglomerates of the Eu₂O₃ nanocrystals.

To demonstrate transparency of the Eu₂O₃ nanocrystal film, an optical micrograph of the patterned silicon substrate was recorded through the nanocrystal film that was deposited on the ITO electrode (as shown in FIG. 4(a). The patterned substrate was clearly visible, which confirmed the formation of highly transparent film. Transmission spectroscopy was performed on the same film to determine its transmission properties in the visible region. Intensity oscillations of transmitted light were seen in the visible transmission spectrum, which were due to Bragg interference because of the thickness of the film (about 110 nm thick). To measure the transmission of the film, an about 500 μm film was deposited using a drop-cast technique. FIG. 4(b) shows the transmission spectrum of the drop-cast film, which reveals high transparency in the visible region (>80%). Considering the high transparency of the thick film, the electrophoretically deposited thin film should have a comparable transmission. High transparency of the film was achieved by minimizing the scattering loss of visible light within the nanocrystal film. The intensity of scattered light off a nanoparticle within the visible region is best expressed by the Rayleigh scattering equation, which is appropriate within the limit x=πd_NC/λ, x<<1. For the average size (15 nm) of agglomerates of the Eu₂O₃ nanocrystals, x ranges between 0.12 and 0.06 in the visible spectral region. Since the nanocrystal films had a transparent appearance instead of hazy (e.g. translucent), the use of Rayleigh scattering theory instead of Mie scattering theory is valid. Rayleigh scattering intensity per particle, I_S, is written as

$\begin{array}{cc}{I}_S={\left(\frac{2\pi }{\lambda }\right)}^4{\left(\frac{n^2-1}{n^2+2}\right)}^2\left(\frac{1+{\cos }^2\theta }{2R^2}\right){\left(\frac{d_{\mathrm{NC}}}{2}\right)}^6{I}_0& \left(1\right)\end{array}$
where λ is the wavelength of the incident light, n is the refractive index of the particle, θ is the scattering angle, R is the distance to the particle from the point of observation, d_NC is the particle diameter and I₀ is the intensity of the incident light. Clearly, the small size of the Eu₂O₃ nanocrystal agglomerates within the film facilitated reduction of the scattering loss of visible light because the scattering intensity is proportional to the sixth power of the particle size. Thus, the small size of the Eu₂O₃ nanocrystal agglomerates was the key to achieving highly transparent films.

The ability to control the thickness of the films made according to the various embodiments of the present invention is extremely important while maintaining film quality. The Hamaker equation (2) correlates the amount of particles deposited (deposit yield, w) during EPD to the electrophoretic mobility (μ), the electric field (E), the electrode area (A), the particle mass concentration in the suspension (C) and the deposition time (t):
w=μEACt  (2)
The electrophoretic mobility (μ) of the particles, suspended in low-dielectric solvents, is related to the zeta potential of the particle (ζ), the solvent viscosity (η), relative permittivity of the solvent (∈_r) and the permittivity of vacuum (∈₀) of the suspension through the Hückel equation (3):

$\begin{array}{cc}\mu =\frac{2{\varepsilon }_0{\varepsilon }_r\zeta }{3\eta }& \left(3\right)\end{array}$

The deposition yield, as stated by the Hamaker equation, is written as

$\begin{array}{cc}w=\frac{2{\varepsilon }_0{\varepsilon }_r\zeta EACt}{3\eta }& \left(4\right)\end{array}$

Since the solvent (hexane) and electrode set-up (deposition area, A=18 mm×13 mm, 5 mm gap) for EPD were the same, the parameters (∈_r, η and A) remained constant. The number of purification steps, employed to purify the nanocrystals, affected the coverage of surface capping ligands on the nanocrystals. Net charges possessed by the nanocrystals in solution are related to the coverage of ligands on the nanocrystal surface (steric stabilization). Hence, the Eu₂O₃ nanocrystals in solution were purified by the same process to maintain a similar zeta potential of the nanocrystals for all EPDs. Thus, the deposition yield (and film thickness) can be controlled via the EPD process parameters such as the electric field (E), the particle concentration (C) and the deposition time (t). For a deposition sequence with a constant applied voltage and a fixed initial concentration, the deposition rate decreases as the deposition time increases [56]. A decreasing particle concentration within the EPD suspension and an increasing voltage drop across the growing film of insulating/semiconducting nanoparticles also decreases the deposition rate for extended deposition times. It was reported that the current density and deposition rate of hydroxyapatite decreased as a function of deposition time [57]. A decreasing current density through the particle suspension is an indication of a decreasing deposition rate. It has been observed that the current density through the Eu₂O₃ nanocrystal suspension prepared according to various embodiments of the present invention dropped at least 80% within ten minutes of the beginning of the deposition run. Since the deposition rate was expected to be low at times beyond fifteen minutes of deposition time, the deposition time fixed at 15 minutes was maintained for all EPD experiments and the applied voltage and the nanocrystal concentration was varied to monitor the uniformity and thickness of the films.

EPD of the Eu₂O₃ nanocrystals was performed at different applied voltages (250, 500, 750 and 1000 V) and with different nanocrystal concentrations (1×10¹⁵, 2×10¹⁵ and 4×10¹⁵ NC cm⁻³) to understand their effect on the thickness and uniformity of the nanocrystal film. Thickness measurements were conducted at five locations on three different samples, and the average thickness was determined with the standard deviation of the thicknesses as the error bar. Hence, the error bar conveys the thickness uniformity of the film. FIG. 5 shows the graph of the nanocrystal film thickness as a function of the applied voltage for different nanocrystal concentrations. The film thickness increased as a function of the applied voltage and nanocrystal concentration, as expected. When the applied voltage was increased, more nanocrystals moved toward the electrodes under the influence of increased electric field and deposited to form films. Similarly, when the nanocrystal concentration was increased, more charged nanocrystals were available for deposition, which led to the formation of thicker films. By performing electrophoretic mobility measurements on the EPD suspensions of different nanocrystal concentrations, it was confirmed that more charged nanocrystals were available for deposition as the nanocrystal concentration increased. FIG. 6 shows that the scattering intensity of the particles increased with nanocrystal concentration for a given electrophoretic mobility. Subsequently, the thickness of the nanocrystal film increased with the EPD process parameters (applied voltage and nanocrystal concentration). During EPD, a constant applied voltage was maintained, but the nanocrystal concentration of the EPD suspension decreased with time as the Eu₂O₃ nanocrystal film grew. The growth of the film slowed as the EPD progressed. The two factors that slowed down the growth were: (a) the increasing voltage drop across the growing film of the insulating Eu₂O₃ nanocrystals and (b) the depletion of charged nanocrystals from the EPD suspension. Since voltage drop across the film increased as the film grew, the effective voltage across the EPD suspension decreased because the applied voltage was constant. For a given nanocrystal concentration, thicker nanocrystal films were deposited when higher applied voltages were employed. The application of higher voltage between the electrodes facilitated an increased effective voltage across the EPD suspension, resulting in thicker films. Since thicker films were deposited with higher applied voltages for a given nanocrystal concentration, the nanocrystal suspension was not entirely depleted of charged nanocrystals. Thus, the increasing voltage drop across the growing Eu₂O₃ nanocrystal film was primarily responsible for restricting growth of the film.

EPD process parameters (applied voltage and nanocrystal concentration) altered the uniformity of the Eu₂O₃ nanocrystal film as illustrated in FIG. 5). For a given nanocrystal concentration, film uniformity decreased (larger error bar) as the applied voltage increased. Also, the thickness uniformity decreased (larger error bar) for higher nanocrystal concentrations for a given applied voltage. Although the films were increasingly non-uniform, we observed a particular pattern in thickness variation. The films were thick towards the edges of the electrode and were thin in the centre of the electrode, which suggested the presence of strong fringe electric fields near the edges of the electrode. Naturally the fringe field increased with applied voltage; therefore, more nanocrystals deposited near the edges of the electrode, increasing the non-uniformity of the film. Also, the non-uniformity of the film increased when the nanocrystal concentration increased. Since the same EPD setup (deposition area: 18 mm×13 mm electrode, 5 mm gap) was employed for all the depositions, variation in the thickness uniformity of the film was purely a result of changes in the EPD process parameters. Thus, the nanocrystal concentration and the applied voltage cannot be increased indefinitely to increase deposition rate or film thickness because they affect the uniformity of the EPD film.

The microscopic morphology and the elemental composition of the EPD films formed according to various embodiments of the present invention were analysed as a function of film thickness, which explained whether the nanocrystals underwent any chemical, geometrical or topological modifications while being deposited under the EPD electric field. It was chosen to interrogate films produced from the highest nanocrystal concentration, 4×10¹⁵ NC cm⁻³, according to one embodiment of the present invention, as they yielded the most substantial deviations from uniformity in the topology, substrate coverage and roughness in the films when assessed at the macroscopic level. It was surmised that such film characteristics would yield the largest changes in microscopic/nanoscale topology, morphology and compositional changes, if any such change existed. AFM imaging and EDS analysis were performed on the four films with different thicknesses, which were deposited at four different applied voltages formed according to various embodiments of the present invention. FIGS. 7(a)-(d) show AFM images of the EPD films deposited at 250 V, 500 V, 750 V and 1000 V, respectively. The films were composed of agglomerates of the Eu₂O₃ nanocrystals, which were approximately 130-160 nm in diameter. These agglomerates formed from 4×10¹⁵ NC cm⁻³ nanocrystal concentration were much larger than the observed agglomerates deposited from the lower 2×10¹⁵ NC cm⁻³ nanocrystal concentration (FIG. 3(b)). The agglomerate size was consistent across individual films and was nearly identical for different applied voltages (FIGS. 7(a)-(d)). The smoothness of all the films was comparable. The RMS surface roughness, determined from an analysis of the AFM images of the films, varied between about 1.6 and 1.8 nm. This roughness was still smaller than the diameter of one nanocrystal. Thus, the films maintained a smooth topography as a function of film thickness/applied voltage.

Additionally, EDS analysis of the films was performed to juxtapose their compositions. EDS analyses were performed on small, cleaved sections of the EPD films placed onto silicon substrates rather than on the original ITO-coated glass substrates. This step was utilized since the contribution of oxygen signal from the substrate dominated the oxygen signal from the Eu₂O₃ nanocrystal films. Silicon substrates were chosen because their EDS peaks do not coincide with the europium and oxygen peaks. FIGS. 7(e)-(h) show the EDS graphs of the EPD films, deposited at 250 V, 500 V, 750 V and 1000 V, respectively. To compare the composition of the nanocrystals, it was monitored the intensity of the oxygen peak (K line: 0.52 keV) relative to the intensity of the europium peak (M line: 5.84 keV). The average ratio of intensities, 2.32±0.13, was within 5% of all four of the intensity ratios, which confirmed that the composition of the nanocrystals in the films did not change as a function of, or because of, the applied voltage. Thus, these analyses confirmed that the morphology, composition and topology of the film at the microscopic level remained consistent as the film thickness increased.

In sum, in one aspect, transparent films of about 2.4 nm diameter Eu₂O₃ nanocrystals were deposited successfully onto conducting substrates from nanocrystal suspensions, prepared in hexane, using the EPD technique according to various embodiments of the present invention. The films comprised agglomerates (about 15 nm) of Eu₂O₃ nanocrystals, which likely formed under the influence of the electric field applied during EPD. The small size of the agglomerates scattered a small fraction of visible light, which reduced light scattering losses, and thus enhanced transparency of the film (>80%) in the visible region. The films were uniform, smooth and densely packed with a packing fraction of about 0.56 (glassy packing regime). The films maintained very low RMS surface roughness (about 1.4 nm). The effect of the EPD process parameters (applied voltage and nanocrystal concentration) on growth of these transparent films was evaluated. The thickness of the nanocrystal films increased with applied voltage and nanocrystal concentration; however, growth of transparent films of the Eu₂O₃ nanocrystals slowed down with deposition time. The voltage drop across the film of insulating Eu₂O₃ nanocrystals played a primary role and the depletion of nanocrystals from the suspension played a secondary role in suppressing the growth of the films. Nonuniformity of the nanocrystal film increased with applied voltage and nanocrystal concentration, which was attributed to the effect of a fringe electric field. Knowledge of the effect of EPD process parameters on the overall quality of the nanocrystal films may prove helpful to the deposition of other nanocrystal systems. Insight gained into the growth of high quality electrophoretically deposited films of the colloidal nanocrystals would be beneficial in the design and production of nanocrystal-based optical, magnetic and electronic devices.

Example 2

Gd₂O₃ Nanocrystal Films

Gadolinium oxide (Gd₂O₃) in its crystalline and amorphous phases has been of research interest as a replacement gate oxide material for silicon dioxide because of its high dielectric constant (κ=14) [58]. Nanocrystals (NCs) of Gd₂O₃ have been investigated for their applications as a magnetic contrast agents [59, 60], and host materials in Eu³⁺- and Tb³⁺-doped light emitting materials [61]. Recently, dielectric studies of amorphous Gd₂O₃ films, embedded with Gd₂O₃ NCs, revealed intriguing charge storage characteristics of the NCs [62]. Similarly, metallic NCs (Au, Ru, Ni, and Co) [63-65] and semiconducting NCs (Si and Ge) [66, 67] have exhibited charge-storage characteristics when they were embedded in the gate oxide layer of a metal-oxide-semiconductor (MOS) structure for non-volatile memory (NVM) applications. NC confined states, the states at the interface of NC-dielectric (i.e. NC surface), and the defect sites inside NCs are responsible for charge-storage behavior [63, 68, 69]. Colloidal NCs may possess similar charge-storage capabilities because of the unpassivated surface states that can arise due to the detachment of some fraction of the nanocrystals' surface capping ligands during cleaning procedure [70-72]. Dielectric studies of films composed entirely of colloidal Gd₂O₃ NCs may provide insight into this subject. An effective technology for the fabrication of casts of particles, electrophoretic deposition (EPD) can produce densely-packed films of colloidal NCs at high deposition rates [70, 73]. According to various embodiments of the present invention, EPD was employed to produce films consisting only of colloidal Gd₂O₃ NCs to be used as the gate oxide layer in MOS architecture. Capacitance-voltage (C-V) measurements of these MOS structures exhibited hysteresis, illustrating the charge-storage capabilities of the films. The dielectric constant of the NC films (κ) was determined from C-V measurements of the MOS structures with different NC film thicknesses. Since the dielectric constant of the NC films depended on the packing density of NCs within the films, κ subsequently was used to determine the NC packing density.

Fabrication of MOS Capacitor Structures and Characterizations.

In one embodiment of the present invention, as shown in the schematic of FIG. 8(a), MOS capacitor structures were fabricated, composed of films of ultra-small colloidal Gd₂O₃ NCs employed as the dielectric oxide layer. The about 2.4 nm diameter Gd₂O₃ nanocrystals were synthesized via a two-stage solution-phase technique and were capped with oleic acid [71]. The as-synthesized NCs were cleaned in ethanol using a precipitation-centrifugation sequence, described elsewhere [71]. After purifying the Gd₂O₃ NCs, they were suspended in hexane and then were deposited onto p-(100) silicon substrates [epi layer: 20-40 Ω·cm and substrate: 0.005-0.025 Ω·cm] via electrophoretic deposition. For EPD, a pair of silicon electrodes (25 mm×13 mm) was mounted in a parallel-plate configuration with a gap of about 5 mm. A DC voltage of 500 V was applied to the electrode pair using a Keithley 6517A electrometer. The voltage was applied for 15 min during the deposition and, subsequently, for 5 min during an air drying step of the film to improve densification of the film [70, 74]. The NCs deposited on both the cathode and the anode. FIG. 8(b) shows an image of the NC film (anode) captured using a Nanoscope III atomic force microscope (AFM). The film was continuous and topologically smooth with root mean square (RMS) roughness of about 1.6 nm, which was smaller than the diameter of the nanocrystals (about 2.4 nm). An image of the nanocrystals acquired with Philips CM 20 transmission electron microscope (TEM) is shown as an inset to FIG. 8(b). It was confirmed the deposition of the Gd₂O₃ NCs by performing energy dispersive spectroscopy (EDS) of the film using a Link ISIS series 300 microanalysis system. Shown in FIG. 8(c), the EDS spectrum of the film exhibits the gadolinium, oxygen, carbon, and silicon peaks, which are present due to the oleic acid-capped Gd₂O₃ NCs on the silicon substrate. To complete the fabrication of the MOS capacitors, aluminum contacts (500 μm diameter and 300 nm thick) were deposited on the Gd₂O₃ NC film via e-beam evaporation of aluminum using a shadow mask. Aluminum was chosen as the gate material because of its suitable work function and cost effectiveness. FIG. 8(d) shows the image, which is a top view, of the MOS capacitors recorded using a Hitachi S-4200 scanning electron microscope (SEM). MOS capacitors were fabricated with different oxide layer (NC film) thicknesses (116±10 nm, 179±10 nm, 276±10 nm, and 397±15 nm), which were verified using a Veeco Dektak 150 surface profiler. To vary thickness of the NC film, EPD suspensions of different NC concentrations (1.0×10¹⁵ NC/cm³, 1.5×10¹⁵ NC/cm³, 2.0×10¹⁵ NC/cm³, and 2.5×10¹⁵ NC/cm³) were employed.

C-V Measurements, and Calculations of the Dielectric Constant (κ) and the Packing Density.

High-frequency C-V measurements of the capacitors were performed at a frequency of 1 MHz and at a sweep rate of 50 mV/s, using a Keithley 590 CV analyzer on a Signatone probe station. The gate voltage was swept from −10 V (accumulation) to +5 V (inversion) and back to −10 V (accumulation). The capacitors were biased at −10 V for 15 min prior to the forward sweep and were biased at +5 V for 1 min prior to the reverse sweep. FIG. 9 shows the C-V characteristics of capacitors fabricated from 116 nm thick NC films, deposited on the anode and cathode. C-V characteristics of both capacitors are similar to that of a typical MOS capacitor with distinct accumulation, depletion, and inversion regions. The MOS capacitors exhibited a clockwise hysteresis in their C-V characteristics as they were biased through the accumulation-inversion-accumulation regions. The observed hysteresis indicated the presence of charge carriers within the NC film. The charge carriers could be immobile charges, arising from the unpassivated surface sites (Gd³⁺ and O²⁻) of the NCs, or mobile charges (electrons or holes), injected into the NC film. The presence of positive charges shifts the flat-band voltage (V_FB) in negative direction, while the presence of negative charges shifts it in positive direction. Assuming no charges in the NC film, the ideal flat-band voltage (V_FB^Ideal) of −0.88 V was based on the work functions of Al and Si and the doping concentration in the epi layer. A larger negative shift in V_FB (ΔV_FB is about −3.92 V, anode) during reverse sweep (inversion-accumulation) than the positive shift in V_FB (ΔV_FB is about 0.05 V, anode) during forward sweep (accumulation-inversion) suggested the presence of more positive charges in the NC film. Electrons were injected into the NC film from the gate electrode in the accumulation region, while electrons were subsequently extracted (equivalent to injection of holes) from the NC film into the gate electrode in the inversion region. To compare the charge-storage in the NC films deposited on the anode and cathode, it was measured the width of the hysteresis window (ΔV) for the two NC films [3.97 V (anode) and 4.19 V (cathode)]. These values were within the statistical uncertainty (±0.13 V) when multiple MOS capacitors were characterized. Similar to other metal [64], semiconductor [66, 67], and insulator [62] NC-embedded MOS capacitor structures, charge-storage was observed in the Gd₂O₃ NC films formed according to various embodiments of the present invention.

FIG. 10 shows C-V characteristics of the MOS capacitors for NC films of different thicknesses. The oxide capacitance, C_OX, in the accumulation region decreased with increased NC film thickness, as was expected. For a given gate dielectric material (typically oxide), the oxide capacitance (in accumulation) has a linear relationship with the inverse of the gate oxide thickness, as stated in equation 1 set forth below:

$\begin{array}{cc}{C}_{\mathrm{OX}}=\frac{A\times {\varepsilon }_{\mathrm{OX}}}{t_{\mathrm{OX}}}& \left(1\right)\end{array}$
In this expression, C_OX is the oxide capacitance (F), A is the gate area (cm²), t_OX is the oxide thickness (cm), and ∈_OX is the permittivity of the oxide material (F/cm). From the thickness and capacitance of the Gd₂O₃ NC film, the permittivity of the NC film can be determined. FIG. 11 shows a graph of the NC film capacitance as a function of the inverse of the NC film thickness for MOS capacitors with different NC film thicknesses. The data exhibited good agreement with the linear trend. The dielectric permittivity of the NC film was extracted from slope of the linear fit, given the area of the gate. The dielectric constant, κ, of the Gd₂O₃ NC film was calculated using the relation, κ=∈_OX/∈₀ and was found to be 3.90±0.06. Since the NC film comprised Gd₂O₃ (κ=14.0), oleic acid (κ=2.5), and air (κ=1.0), the effective dielectric constant of the NC film depended on the volumetric fractions of each component in the film. Good agreement between the data and the liner fit suggested that all of the NC films, cast from solutions with different NC concentrations, possessed comparable NC packing fractions. It was calculated the volumetric packing fractions of the NC film using a three-component Bruggeman model for the dielectric constant (Equations 2 and 3):

$\begin{array}{cc}{f}_{\mathrm{air}}\frac{{\kappa }_{\mathrm{air}}-{\kappa }_{\mathrm{NC}\mathrm{film}}}{{\kappa }_{\mathrm{air}}+2{\kappa }_{\mathrm{NC}\mathrm{film}}}+f_{\mathrm{oleic}}\frac{{\kappa }_{\mathrm{oleic}}-{\kappa }_{\mathrm{NC}\mathrm{film}}}{{\kappa }_{\mathrm{oleic}}+2{\kappa }_{\mathrm{NC}\mathrm{film}}}+f_{{\mathrm{Gd}}_2{O}_3}\frac{{\kappa }_{{\mathrm{Gd}}_2{O}_3}-{\kappa }_{\mathrm{NC}\mathrm{film}}}{{\kappa }_{{\mathrm{Gd}}_2{O}_3}+2{\kappa }_{\mathrm{NC}\mathrm{film}}}=0& \left(2\right)\\ f_{\mathrm{air}}+f_{\mathrm{oleic}}+f_{{\mathrm{Gd}}_2{O}_3}=1& \left(3\right)\end{array}$
In the expression, volume fractions of air, NC film, oleic acid, and Gd₂O₃ are given as f_air, f_{NC film}, f_oleic, and f_Gd2O3, respectively. Dielectric constants of air, NC film, and Gd₂O₃ are given as κ_air, κ_{NC film}, κ_oleic, and κ_Gd2O3, respectively. Based on the coverage of oleic acid on the surface of a spherical NC core, a relationship was formed between the volumetric fractions of the oleic acid surfactant and the Gd₂O₃ NC core as stated in equation 4, where R₁ is radius of the Gd₂O₃ NC core (R₁=1.2 nm±0.1), and R₂ is the radius of NC core plus thickness of the oleic acid layer (0.3±0.1 nm):
f_oleic=f_Gd2O3[(R₂/R₁)³−1]  (4)
Volumetric fractions, f_Gd2O3=0.34±0.02, f_air=0.34±0.08, and f_oleic=0.32±0.10, were calculated from equations 2-4. The summed packing fraction for the nanocrystals (Gd₂O₃ NC core plus oleic acid) is 0.66±0.08 and resides within the glassy packing regime for closely packed spheres [75]. Thus, EPD can produce densely packed, glassy films of ultra-small nanocrystals that exhibit potential charge storage capabilities, surmised from their packing density and their effective dielectric constant.
Dielectric Properties of the Colloidal Gd₂O₃ NC Films.

Accordingly, in another aspect, MOS capacitor structures with colloidal Gd₂O₃ NC film as oxide layer were fabricated according to various embodiments of the present invention. Uniformly deposited films of the purified Gd₂O₃ NCs were produced via electrophoretic deposition. C-V measurements of the MOS capacitors exhibited clockwise hysteresis that suggested charge-storage within the NC films. The NC films, deposited on the anode and cathode, had similar charge-storage properties. NC films with different thicknesses showed charge-storage behavior. Dielectric constant (κ=3.90) of the NC films was calculated from the C-V measurements of the MOS capacitors. Packing density of the NCs within the film (0.66±0.08) was calculated from the dielectric constant of the NC film and was found to be within glassy-packing regime, as expected for the films deposited via EPD.

The foregoing description of the exemplary embodiments of the invention has been presented only for the purposes of illustration and description and is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many modifications and variations are possible in light of the above teaching.

The embodiments were chosen and described in order to explain the principles of the invention and their practical application so as to enable others skilled in the art to utilize the invention and various embodiments and with various modifications as are suited to the particular use contemplated. Alternative embodiments will become apparent to those skilled in the art to which the present invention pertains without departing from its spirit and scope. Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing description and the exemplary embodiments described therein.

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Claims

1. A metal-oxide-semiconductor (mos) capacitor, comprising:

(a) a silicon substrate having a first surface;

(b) a film of lanthanide oxide nanoparticles functioning as a charge storage of the mos capacitor and formed by electrophoretically depositing pre-formed lanthanide oxide nanoparticles directly on the first surface of the silicon substrate; and

(c) an aluminum film formed on the film of lanthanide oxide nanoparticles.

2. The metal-oxide-semiconductor (mos) capacitor of claim 1, wherein the silicon substrate comprises p-type silicon.

3. The metal-oxide-semiconductor (mos) capacitor of claim 2, wherein the first surface of the silicon substrate is a p-(100) surface of silicon.

4. The metal-oxide-semiconductor (mos) capacitor of claim 1, wherein the lanthanide oxide nanoparticles comprise europium oxide (Eu₂O₃) nanoparticles or gadolinium oxide (Gd₂O₃) nanoparticles.

5. The metal-oxide-semiconductor (mos) capacitor of claim 1, wherein the film of lanthanide oxide nanoparticles has a thickness ranging from about 50 to about 500 nm.

6. The metal-oxide-semiconductor (mos) capacitor of claim 1, wherein the aluminum film has a thickness of about 300 nm.

7. The metal-oxide-semiconductor (mos) capacitor of claim 1, wherein the aluminum film is formed on the film of lanthanide oxide nanoparticles using electron-beam evaporation.

8. The metal-oxide-semiconductor (mos) capacitor of claim 1, wherein the film of lanthanide oxide nanoparticles comprises randomly close-packed lanthanide oxide nanoparticles with a packing density of about 66%.